Branched organopolysiloxanes containing terminal hydroxy groups



United States Patent Ofi ice 3,488,372 Patented Jan. 6, 1970 3,488,372 BRANCHED ORGANOPOLYSILOXANES CONTAIN ING TERMINAL HYDROXY GROUPS Gerd Rossmy, Altendorf (Ruhr), and Jakob Wassermeyer,

Essen, Germany; said Rossmy assignor to Th. Goldschmidt A.G., Essen, Germany N Drawing. Filed July 22, 1964, Ser. No. 384,530 Claims priority, applicatign (iermany, July 26, 1963,

Int. Cl. C07f 7/18; (108g 22/00; C14c 9/00 US. Cl. 260448.2 19 Claims ABSTRACT OF THE DISCLOSURE Process for the preparation of organopolysiloxanes havmg terminal hydroxyl groups. An organopolysiloxane 0f the general formula R is monovalent hydrocarbon;

X is halogen;

x has a value of from 1.5 to 2.1;

y has a value of from 0.5 to 1.2;

2 has a value of from 0.001 to 1.2; and y+ z) is reacted with ammonia, primary amines or secondary amines. The reaction product thus obtained is then subjected to hydrolysis The novel compounds find utility as impregnating agents for paper and leather and in the manufacturing of polyurethane foams.

CROSS-REFERENCE TO PRIOR APPLICATIONS This is a continuationin-part of application Ser. No. 168,833, filed Jan. 25, 1962, now Patent No. 3,183,254, which application in turn was a continuation-in-part of application Ser. Nos. 35,138 and 35,139 filed June 10, 1960, both now abandoned, and 108,755, filed May 9, 1961, now Patent No. 3,115,512. The disclosure of column 1, line 1 to column 5, line 46 of said Patent No. 3,183,254 is specifically incorporated herein as if set forth in full.

SUMMARY OF THE INVENTION This invention generally relates to organosilicon compounds and processes for their preparation. In particular, the invention is directed to a process for preparing organopolysiloxanes having terminal hydroxyl groups. The

invention is also concerned with novel organopolysiloxanes having terminal hydroxyl groups as obtained by the inventive process.

organosiloxanes with terminal hydroxyl groups have found many uses and applications in industry. Thus, for example, such organosiloxanes have been suggested as the active component in preparations for rendering leather hydrophobic. Further, such organosiloxanes are com-.

practiced procedures are not properly reproducible so that the properties and quality of the organopolysiloxanes obtained vary considerably with different batches.

Accordingly, it is a primary object of this invention to provide a process for the preparation of organopolysiloxanes having terminal hydroxyl groups which is readily reproducible and which yields such organopolysiloxanes with uniform characteristics and quality.

It is also an object of this invention to provide a process for the manufacture of organopolysiloxanes having terminal hydroxyl groups which is easy to carry out, less expensive and more economical than prior art processes.

Another object of this invention is to provide novel organopolysiloxanes having terminal hydroxyl groups.

Generally it is an object of this invention to improve on the art of organopolysiloxanes having terminal hydroxyl groups.

Briefly, and in accordance with this invention, organopolysiloxanes of the general polymer Formula I are reacted with ammonia and/or primary or secondary amines and the reaction products obtained are subsequently subjected to hydrolysis.

In Formula I, R stands for monovalent hydrocarbon, preferably methyl. A mixture of hydrocarbon groups, some of which may be substituted, is also feasible.

X stands for halogen, preferably chlorine, which, how ever, partially may be replaced by the group OSO H;

x has a value of from 1.5 to 2.1, preferably 1.85 to 2.0;

y has a value of from 0.5 to 1.2, preferably 0.75 to 1.15;

1 has a value of from 0.0001 to 0.2, preferably 0.001 to 0.1; and

It will thus be realized that in accordance with the Inventive process, the polysiloxanes of Formula I are first reacted with the ammonia and/0r primary or secondary amines. In this manner, siloxanes are obtained which are linked by Si-N-Si groups and/ or which have end blocking groups. These siloxanes are thereafter hydrolyzed.

A particular advantage of the inventive process resides in the fact that organosiloxanes with terminal hydroxyl groups are formed which, in regard to the polymer distribution and in regard to the distribution of different siloxane units in the polymer molecule, correspond to the statistical equilibrium, or at least very closely approach the statistical equilibrium. It will be realized that in referring to polymer distribution which corresponds to the statistical equilibrium, the condensation tendency of those organosiloxanes with terminal hydroxyl groups has, of course not been considered. This means, in other words, that the equilibrium of the polymer distribution corresponds to that of the starting compounds, each X atom of the starting compound merely being replaced by one hydroxyl group while each S0 group of the starting compound is replaced by two hydroxyl groups. In referring to this polymer equilibrium, the hydroxyl group is thus being regarded as a non-reacting grouping. This has not been possible with branched siloxanes as they are known in the art while, with regard to linear siloxanes, this has only been feasible to a very limited extent and by means of very cumbersome processes.

It has surprisingly been ascertained that in the inventive process the hydrolysis proceeds quantitatively without significant condensation of the Si-OH groups to Si-O-Si groups.

According to a preferred embodiment of the inventive process, the reaction of the siloxane of Formula I with ammonia or amine is carried out in the presence of an inert solvent. This is of particular importance if the siloxane used as starting compound is of a branched nature and/ or if ammonia or a primary amine is used as reactant. With branched siloxanes, it is oftentimes advantageous to 3 4 use a secondary amine in order, in this manner, tomain- It will be appreciated that the polymer Formula I only tain the molecular weight of the reaction products within represents the average composition and structure of the certain limits. A person skilled in this art will be able starting materials to be used in accordance with this ineasily to decide for each individual case whether it is more vention. Examples for such starting polysiloxanes repreadvantageous and economical to use the inexpensive am- 5 sented and embraced by the general Formula I are commonia or primary amine, and to counteract the cross linkpounds of the Formula II ing effect of these reactants by using larger amounts of solvent or instead to use a relatively expensive secondary R amine with a lesser expenditure of solvent. X- SiO- -SiOS-O- -di-X Experience has demonstrated that particularly favorable g, l 6 results are obtained if the reaction of the polysiloxane of n Formula I is carried out with amines of the general for- I i f l R and X have h above i mula n has a value of from 3 to 100, preferably from 8 to 30;

R and in has a value of from 0.01 to 2, preferably from 0.05

It follows that not each molecule has to contain a silylwherein R is alkyl of 1 to 5 carbon atoms and R is the sulfate group. The best value for m has to be ascertained same as R or is hydrogen. for each system.

It is assumed that the SiX and the Si-O-S groups Examples for further compounds which are embraced of the starting siloxane each react with one HN group by the general average Formula I may be represented by under formation of Si--N linkages. However, if amthe following Formula III.

monia is used as the reactant, at the most two NH- In this formula, R and X have the above-indicated groups in the molecule will react in this manner. Concernmeaning. A portion of the X groups, particularly 5 to ing the reactive NH groups, amounts are used which are 40% thereof, is replaced by at least equivalent to the acid groups of the starting siloxane. In many instances, however, it is of advantage to use g a certain excess of NH groups. In calculating the amount to be used, it should be considered, however, that for the neutralization of the amount of acids HX and H 50 which is theoretically liberated, 1 or 2 moles of ammonia g p so that ne 04 g p rep s wo X gr ups.

or amine, respectively, are also required. R stands for hydrocarbon and is preferably methyl,

The removal of these ammonium or alkylammonium ethyl, vinyl or phenyl;

salts is advantageously carried out during the subsequent a has a value of from 1 to 20, preferably of from hydrolysis. Preferably, an excess of water is used which is 3 to 10; and

large enough to cause solution of all the salts. In order to b has a value of from 1 to 20, preferably of from obtain a complete reaction, it is advantageous to carry out 1 to 5.

the hydrolysis in an acid medium, preferably in aqueous Also, siloxanes which are derived from the siloxanes solutions of weak acids. A particularly advantageous pH of Formula III by the replacement of two SiX groups range is the range 53. Acetic acid or formic acid are recby one Si-O-Si group correspond to the general average ommended weak acids for this purpose. It is also recom- Formula I and thus are embraced within the scope of the mended to add the acid in such quantities that at least 1 inventive starting substances.

mole of acid is available for each ammonia or amine A further group of starting compounds may be repregroup bound to siloxane. If necessary, stronger acids can sented by the following Formula IV be employed. However, in that event, special care has to In Formula IV, R, X, a and b have the same meaning be taken in order to prevent pronounced condensation of as in Formula III.

the S1-OH groups. This can be done by asuitable choice Polysiloxanes which are obtained by reacting comof the amount of solvent and/or by rapid neutralization of pounds of Formula III in the inventive manner are novel any excess acld 1n the system. and may be represented by the following formula:

The same applies to compounds formed by the reaction of compounds of Formula IV. These novel compounds may be represented by the following formula It will be noted that the novel compounds obtained from compounds of Formulas III or IV are identical with the starting compounds except that the X group has been replaced by OH. These novel compounds have extraordinary properties. Although these novel compounds generally are reasonably viscous liquids, they can readily be converted into a resin-like state by curing. They are particularly suitable as impregnation agents for paper and leather. This is so because they can be readily used for this purpose and have an excellent action in this respect. The consistency of the compounds makes it possible to dispense them through a nozzle by gas pressure and, for this reason, it is feasible to package and ship the compounds in pressurized containers. The novel compounds also find utility in the foaming of polyurethane. If used for this purpose, it is possible to obtain a pore structure of the foam which simulates the pore structure of natural sponge.

The value of z in Formula I is dependent on the constitution of the average molecule. The higher the value of z, the more rapid does the equilibration of the siloxane take place. However, the average molecular weight will then also be higher. With branched siloxanes, it is oftentimes advantageous to choose a smaller 2 value and consequently to equilibrate for a longer period. Gelling may take place if the 2 value is too high.

The invention will now be described by several examples, it being understood that these examples are given by way of illustration and not by way of limitation and that many changes may be effected without afiecting in any way the scope and spirit of this invention as recited in the appended claims.

EXAMPLE I The starting material was a siloxane which essentially can be represented "by Formula III, wherein a=6.17, b=3, R and R=CH and X=chlorine, 20% of all chlorine atoms being replaced by 80.; groups in such a manner that one group replaces two SiCl groups. The acid content of the siloxane was 1.84 VaL/g. 200 grams of this siloxane were dissolved in 200 milliliters of CH Cl A solution of 56.5 grams of diethylamine (5% excess) in 100 milliliters of CH Cl was added in dropwise manner to the siloxane solution. The reaction product obtained was washed twice with water and in doing so, the entire salt amount in the reaction mixture was dissolved. About 90 milliliters of CH Cl were thereafter removed by distillation. 368.2 grams of a clear methylene chloride solution remained. This solution contained 0.22% by weight of OH and 0.88% by weight of N in the form of acetic. The mixture thus obtained was stirred for five hours. After separation of the aqueous phase and distilla- 6 tion of about 10 milliliters of CH CI 92.5 grams of a clear solution remained. This solution contained 1.4% by weight of OH in the form of Si-OH groups (corresponding to 75% of the theoretical amount.) The solution was stable, without any change, for several Weeks. The solution is suitable, for example, in combination with zirconium butoxide and/or titanium butoxide, as an impregnating agent for leather.

EXAMPLE II This example was carried out with an equilibrated siloxane which in its basic or average composition corresponded to the Formula III (R and R=CH a=5.4l and b=11, 15% of all chlorine atoms being replaced by 80.; groups; acid content upon titration 1.956 X10- val./g.). 711 grams of this equilibrated siloxane were dissolved in 1100 milliliters of methylene chloride. 214 grams of diethylamine were added to the solution under stirring and cooling. The precipitated salt was separated by the addition of 400 milliliters of water. Thereafter, 700 milliliters of water and subsequently 87.6 grams of acetic acid were added to the system. Upon separation of the aqueous phase, the residue was repeatedly washed with water. After removal of the methylene chloride by distillation, 690 grams of a reasonably viscous product remained. Viscosity: 42.7 cp. (20 C.) the OH-content (determined by the isocyanate method) was 3.57%. The theoretical amount of OH for a siloxane of Formula III with the indicated meaning of the symbols in which all chlorine atoms and 80.; groups are replaced by hydroxyl groups would be 3.85%

EXAMPLE III The starting material was an equilibrated siloxane which in its basic structure can be represented by Formula III (R and R=CH a:6.l7 and 1;:3, X=Cl, of which 15% are replaced by 80.; groups). 2000 grams of this equilibrated siloxane in solution with 3000 milliliters of methylene chloride were reacted with 564 grams of diethylamine and subsequently with water-acetic acid in analogous manner as described in Example II. After processing in the manner described in Example II, 1910 grams of a siloxane having a viscosity of 215 cp. (20 C.) were obtained. The DH content of the final product was 3.45%. The theoretical amount would be 3.55% if all X groups were replaced.

EXAMPLE IV The starting material in this example is a dimethylsiloxane having terminal chlorine groups of which 10% are substituted by 50.; groups. The acid content of the siloxane was 1.793 l0* val./g. 500 grams of this siloxane were dissolved in 750 milliliters of methylene chloride. Thereafter, ammonia was introduced into the solution at room temperature and under stirring. The introduction of the ammonia was performed within 45 minutes until the alkaline reaction of the system. The mixture thus obtained was then left to stand for an additional minutes at 40 C. The precipitated salt was separated by means of 300 milliliters of water. The methylene chloride phase was therefore stirred with 500 milliliters of water and 29.6 grams of acetic acid. Upon separation of the aqueous phase, the residue was washed twice with water and finally the methylene chloride was removed by distillation. The remaining dimethylpolysiloxane (455 grams) exhibited a viscosity of 37.2 cp. (20 C.) and had a hydroxyl group content of 3.45% by weight.

The siloxanes prepared according to Examples II-IV are, for example, suitable as de-foaming agents for aqueous-alcoholic systems and also as impregnating agents for textiles, paper and leather for imparting such materials with hydrophobic and adhesive properties.

While specific embodiments of the invention have been shown and described in detail to illustrate the application of the inventive principles, it will be understood that the invention may be embodied otherwise without departing from such principles.

EXAMPLE V The starting material was an equillibrated siloxane mixture which in its basic structure can be represented by Formula 1H, R=CH R=vinyl, a:3, b=1, X=Cl, of which 12% are substituted by 80.; groups. The acid content of the siloxane was determined to be 3.545 10 va1./g. 100 grams of this siloxane in solution with 150 milliliters of methylene chloride were mixed with 1 gram hydrazine sulfate and then reacted with 5444 grams diethylamine and subsequently with water-acetic acid in analogous manner described in Example II. 90 grams of a siloxane having a viscosity of 107 cp. at 20 C. were obtained. The OH-content was 6.27%. (Theoretical amount: 6.45%.) 1

EXAMPLE VI The starting material was an equilibrated siloxane which in its basic structure can be represented by Formula IV, R=CH a=6.1, X=Cl, of which 21% are substituted by 80.; groups. The acid content of the siloxane was deter- 9 4. A compound as claimed in claim 3, wherein the majority of the R groups stand for methyl.

5. A process for the preparation of organopolysiloxanes having terminal hydroxyl groups, which comprises reacting an organopoplysiloxane of the general formula R is monovalent hydrocarbon;

X is halogen;

x has a value of from 1.5 to 2.1;

y has a value of from 0.5 to 1.2;

z has a value of from 0.001 to 1.2; and

with a member selected from the group consisting of ammonia, primary amines and secondary amines, subjecting the reaction product thus obtained to hydrolysis.

6. A process as claimed in claim 5, wherein R is methyl.

7. A process as claimed in claim 5, wherein R is a mixture of monovalent hydrocarbon and substituted monovalent hydrocarbon.

8. A process as claimed in claim 5, wherein X is chlor- 9. A process as claimed in claim 5, wherein a portion of X is constituted by the group OSO H.

10. A process as claimed in claim 5, wherein x has a value of from 1.85 to 2.0.

11. A process as claimed in claim 5, wherein y has a value of from 0.75 to 1.15.

12. A process as claimed in claim 5, wherein z has a value of from 0.001 to 0.1. I

13. A process for the preparation of organopolysiloxanes having terminal hydroxyl groups which comprises reacting organopolysiloxanes of the general formula wherein R is methyl, X is chlorine, x has a value of from 1.85 to 2.0; y has a value of from 0.75 to 1.15; 2 has a value of 0.001 to 0.1; and 4 (x+2y+2z) 2, with a member selected from the group consisting of ammonia.

wherein R and R stand for hydrocarbon, a=1 to 20 and b=1 to 20.

2. A compound as claimed in claim 1, wherein the maprimary amines and secondary amines, and subjecting the reaction product thus obtained to hydrolysis.

14. A process as claimed in claim 13, wherein a porjority of the R groups is methyl and R is selected from 0 tion of the chlorine atoms is replaced by -OSO H.

the group consisting of methyl, ethyl, vinyl and phenyl, a=3 to 10 and b=1 to 5.

3. A compound of the average formula wherein R is hydrocarbon, a:1 to 20 and b=1 to 20.

15. A process as claimed in claim 5, wherein the reaction with said member is carried out in the presence of an inert solvent.

16. A process as claimed in claim 15, wherein the solvent is CH Cl 17. A process as claimed in claim 5, wherein the hydrolysis is carried out at a pH value in the acidic range of 23.

18. A process as claimed in claim 5, wherein the hydrolysis is carried out in an aqueous solution containing a member selected from the group consisting of acetic acid and formic acid.

19. A process as claimed in claim 5, where said member is an amine of the general formula /NH R! in which -R is alkyl of from 1 to 5 carbon atoms and R 3,183,254 5/1965 Rossmy et al 260-448.2

OTHER REFERENCES Eaborn, Organosilicon Compounds, Academic Press Inc., New York, NY. (1960), pp. 228, 229, 345.

TOBIAS E. IJEVOW, Primary Examiner P. F. SHAVER, Assistant Examiner US. 'Cl. X.R. 

